CN116656041A - Dynamic vulcanization low-temperature-resistant high-impact-resistant polypropylene alloy and preparation method thereof - Google Patents
Dynamic vulcanization low-temperature-resistant high-impact-resistant polypropylene alloy and preparation method thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 79
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 79
- -1 polypropylene Polymers 0.000 title claims abstract description 67
- 239000000956 alloy Substances 0.000 title claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 34
- 238000004073 vulcanization Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920001971 elastomer Polymers 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 35
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 34
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 34
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 34
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001119 stannous chloride Substances 0.000 claims abstract description 34
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 34
- 239000008117 stearic acid Substances 0.000 claims abstract description 34
- 239000011787 zinc oxide Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 24
- MCPSMQGVSYDFLC-UHFFFAOYSA-N formaldehyde;2-octylphenol Chemical compound O=C.CCCCCCCCC1=CC=CC=C1O MCPSMQGVSYDFLC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 16
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 32
- 239000003963 antioxidant agent Substances 0.000 claims description 27
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 4
- 235000014692 zinc oxide Nutrition 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 description 14
- 229920002943 EPDM rubber Polymers 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a dynamic vulcanization low-temperature-resistant high-impact-resistant polypropylene alloy which comprises the following components in parts by weight: polypropylene: 70-90 parts by weight; ethylene-propylene ternary rubber: 5-25 parts by weight; thermoplastic elastomer: 5-15 parts by weight; octyl phenol-formaldehyde cured resin: 0.1-3 parts by weight; stannous chloride: 0.008-0.36 parts by weight; zinc oxide: 0.1 to 0.75 weight portions; stearic acid: 0.05-0.375 parts by weight; the thermoplastic elastomer is at least one of a styrene-hydrogenated isoprene copolymer or a styrene-hydrogenated isoprene-styrene copolymer. The invention adopts SEP or SEPS with higher low-temperature toughening efficiency to improve the low-temperature toughness of the material, and simultaneously adopts octyl phenolic resin as the materialThe ethylene-propylene ternary rubber is dynamically vulcanized by a vulcanizing agent to improve the strength of the material, and the notch impact strength of the material at minus 30 ℃ is up to 50kJ/m 2 Under the condition of ensuring that the room temperature tensile strength of the material is not lower than 30MPa, the rigidity and toughness balance of the material is realized.
Description
Technical Field
The invention relates to a dynamic vulcanization low-temperature-resistant high-impact-resistant polypropylene alloy and a preparation method thereof.
Background
The polypropylene (PP) has the advantages of light weight, environmental protection, no toxicity, good comprehensive performance and the like, and is widely applied to the fields of household appliances, automobiles, daily use, chemical industry and the like. However, PP tends to exhibit brittleness due to its molecular structure, especially brittle failure in low temperature (or high speed) environments, thereby limiting its application in certain extreme scenarios. Therefore, it is necessary to toughen and modify PP. Common toughening methods include: adding elastomer toughening agent, inorganic particle toughening agent, beta-nucleating agent toughening, dynamic vulcanization toughening and the like. However, although the common toughening method has a remarkable effect on improving the room temperature toughness of PP, the toughening method has no remarkable effect on the low temperature toughness (-20 ℃ below) of PP. On the other hand, the dynamic vulcanization toughening often needs to simultaneously introduce the elastomer, so the toughening effect is relatively good. However, when the dynamic vulcanizing agent is a peroxide vulcanizing agent, the peroxide is extremely easy to cause degradation of the PP in the high-temperature processing process of the PP, so that the toughening effect is limited, and the strength of the material is possibly reduced. When the dynamic vulcanizing agent is sulfur, the finally obtained product has darker color and pungent smell, and limits the application of the dynamic vulcanization toughening PP. In addition, the material vulcanized by sulfur is easy to generate reversion phenomenon in the secondary processing process, so that the material performance is reduced. Therefore, for toughening the PP, there is a need to develop a toughening means which is nontoxic, odorless, suitable for secondary processing and capable of effectively improving the low-temperature toughness of the PP.
CN 113912948A discloses a polypropylene nanocomposite with low-temperature toughness and rigidity-toughness balance and a preparation method thereof. In the method, the elastomer and the nano silicon dioxide cooperate, and the dynamic vulcanization technology is combined, so that the material can be toughened at low temperature, and has good low-temperature toughness at ultralow temperature (-30 ℃). However, the vulcanizing agent adopted in the method is a peroxide vulcanizing agent, for example, the production process is poorly controlled, and the degradation of PP molecules is easily caused in the processing process, so that the performance of the final product is greatly fluctuated. On the other hand, the method needs to introduce nano silicon dioxide particles at the same time, and has high cost.
Polymer 112 (2017) 318-324 discloses a method for toughening PP with Ethylene Propylene Diene Monomer (EPDM) and SEP, which has the problem that up to 44% by mass of elastomer is required to convert the brittle-ductile transition temperature (T bd ) Reduced to-30 ℃ and has a notched impact strength of about 20kJ/m at-30 DEG C 2 The tensile strength at room temperature was about 9MPa. Due to the large elastomer consumption, the material cost is increased, and meanwhile, the strength of the material at room temperature is far lower than that of common PP and modified products thereof (about 20-30 MPa).
The invention comprises the following steps:
the invention aims to provide a dynamic vulcanized low-temperature-resistant high-impact-resistant polypropylene alloy and a production and preparation method thereof.
The technical scheme adopted by the invention is as follows:
the dynamic vulcanized low-temperature-resistant high-impact-resistant polypropylene alloy comprises the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion.
The thermoplastic elastomer is one or two of styrene-hydrogenated isoprene copolymer (SEP) or styrene-hydrogenated isoprene-styrene copolymer (SEPS).
The octyl phenol aldehyde vulcanized resin is thermal reaction type octyl phenol aldehyde vulcanized resin, and methylene ether bonds (-CH) are adopted between alkylphenols in the molecular structure 2 OCH 2 (-) and/or methylene linkages (-CH) 2 (-) are connected.
Commercially available octyl phenol-formaldehyde vulcanized resins such as SP-1045, HY-2045 and the like can be selected.
The molecular two ends of the octyl phenol-formaldehyde vulcanized resin are mainly terminated by hydroxymethyl active groups. Preferably, the mass content of the hydroxymethyl active group is 5 to 20%, more preferably 8 to 15%.
Further, the low-temperature-resistant high-impact-resistant polypropylene alloy can also contain a small amount of antioxidant, and comprises the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion
An antioxidant: 0.01 to 5 parts by weight.
The antioxidant is preferably one or two of antioxidant 1010 and antioxidant 1076.
Preferably, the low-temperature-resistant high-impact-resistant polypropylene alloy comprises the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion
An antioxidant: 0.01 to 5 parts by weight.
Further, it is more preferable that the low temperature and high impact resistant polypropylene alloy consists of the following components in parts by weight:
polypropylene: 75-85 parts by weight
Ethylene-propylene ternary rubber: 15 to 25 parts by weight
Thermoplastic elastomer: 8 to 15 weight portions
Octyl phenol-formaldehyde cured resin: 0.5 to 2 weight portions
Stannous chloride: 0.05 to 0.2 part by weight
Zinc oxide: 0.3 to 0.7 part by weight
Stearic acid: 0.15 to 0.35 part by weight
An antioxidant: 0.05 to 2 parts by weight.
The amount of the octyl phenol resin is preferably 2 to 12% by mass, more preferably 4 to 10% by mass, of the ethylene-propylene ternary rubber.
The stannous chloride is preferably used in an amount of 8-12% by mass of the octyl phenol resin, more preferably 10%.
The zinc oxide is preferably used in an amount of 2 to 3% by mass, more preferably 2.5% by mass, based on the mass of the ethylene-propylene-diene rubber.
The amount of stearic acid is preferably 1 to 1.5% by mass, more preferably 1.25% by mass, based on the mass of the ethylene-propylene-diene rubber.
The invention also provides a preparation method of the low-temperature-resistant high-impact-resistant polypropylene alloy, which is the following method (one) or the following method (two):
the method comprises the following steps:
(1) According to the raw material proportion, polypropylene, ethylene-propylene ternary rubber and a thermoplastic elastomer are fed, and part of stearic acid, part of zinc oxide, part of stannous chloride and part of antioxidant are fed, and are melt-blended by an internal mixer or melt-extruded and granulated by a double screw extruder, so that an intermediate material is obtained;
(2) And (3) melting, extruding and granulating the intermediate material, the rest of stearic acid, the rest of zinc oxide, the rest of stannous chloride and the rest of antioxidant by using a double-screw extruder, putting octyl phenol-formaldehyde vulcanized resin into a melting section of the double-screw extruder for dynamic vulcanization, and extruding and granulating to obtain the low-temperature-resistant high-impact-resistant polypropylene alloy.
Further, in the step (1), the amounts of the partial stearic acid, the partial zinc oxide, the partial stannous chloride and the partial antioxidant which are preferably added are respectively 50-100% of the total stearic acid, the total zinc oxide, the total stannous chloride and the total antioxidant, and the rest stearic acid, the rest zinc oxide, the rest stannous chloride and the rest antioxidant are added in the step (2);
when the dosages of the part of stearic acid, the part of zinc oxide, the part of stannous chloride and the part of antioxidant added in the step (1) are respectively 100% of the dosages of all stearic acid, all zinc oxide, all stannous chloride and all antioxidant, namely, the whole stearic acid, all zinc oxide, all stannous chloride or all antioxidant is added in the step (1), the corresponding raw materials are not needed to be added in the step (2).
When all stearic acid, all zinc oxide, all stannous chloride and all antioxidants are added in step (1), the octyl phenol-formaldehyde cured resin of step (2) can be fed together with the intermediate material.
The temperature of the internal mixer melt blending in the step (1) is preferably 140-230 ℃, and the temperature of the twin-screw extruder melt extrusion granulation is preferably 140-230 ℃.
Typical extrusion processes for a preferred twin screw extruder are: the temperature of the conveying section is 90-180 ℃, the temperature of the melting section is 140-230 ℃, the temperature of the homogenizing section is 160-230 ℃, the temperature of the die is 160-230 ℃ and the rotating speed of the screw is 50-150 rpm.
Method (two) one-step method:
for a double-screw extruder which is provided with an independent metering feeding system and can realize sectional feeding, a step method is not needed, and the adopted single-step method comprises the following steps:
the polypropylene, the ethylene-propylene ternary rubber and the thermoplastic elastomer are fed into a main feeding port of a double-screw extruder according to the measurement; metering stearic acid, zinc oxide and stannous chloride from a main feeding port of a double-screw extruder or from a secondary feeding port of a barrel which is spaced from the main feeding port by at least 1 section; stearic acid, zinc oxide and stannous chloride can be fed from the same secondary feeding port or respectively fed from 2-3 secondary feeding ports, and at least 1 section of cylinder is arranged between every two adjacent secondary feeding ports; feeding octyl phenol-formaldehyde vulcanized resin from a third feeding port arranged in the melting section or the homogenizing section according to the measurement; the third feeding port and the last secondary feeding port are separated by at least 2 sections of cylinders; when the antioxidant is used, the antioxidant can be fed from any feeding port; finally, the low-temperature-resistant high-impact-resistant polypropylene alloy is obtained through one-time extrusion.
Further, the method is extrusion granulation at a temperature of 140-230 ℃.
Still further, a typical extrusion process is preferred: the temperature of the conveying section is 90-180 ℃, the temperature of the melting section is 140-230 ℃, the temperature of the homogenizing section is 160-230 ℃, the temperature of the die is 160-230 ℃ and the rotating speed of the screw is 50-150 rpm.
The low-temperature-resistant high-impact-resistant polypropylene alloy provided by the invention can be used for preparing materials such as automobile bumpers, washing machine liners, refrigerator liners and the like, and is suitable for application in application scenes with excellent low-temperature (or high-speed) impact resistance.
The invention has the beneficial effects that:
1. SEP and/or SEPS capable of effectively improving low-temperature toughness of the material are/is selected as auxiliary toughening modifier of PP, and the auxiliary toughening modifier is matched with ethylene-propylene ternary rubber, so that impact toughness of the PP at low temperature can be remarkably improved.
2. The phenolic resin is selected as the vulcanizing agent of the ethylene-propylene ternary rubber, so that the degradation of a PP matrix can be avoided, and the finally obtained material is almost odorless, has good heat resistance and does not generate reversion.
3. The nano silicon dioxide is not needed, and any inorganic filler is not needed, so that the material cost can be effectively reduced.
4. The ethylene-propylene ternary rubber is dynamically vulcanized, so that the elastomer consumption can be effectively reduced, and the PP content of the matrix of the whole material is ensured to be far higher than the elastomer content after vulcanization. By adopting the strategy, even after vulcanization, the material can still be melted at high temperature, has better fluidity, and avoids the problem that the polypropylene vulcanized by the common vulcanizing agent is difficult to process secondarily.
5. The invention can greatly reduce the elastomer consumption when realizing better low-temperature impact performance, so that the tensile strength of the material is obviously increased, and the material strength and toughness are well balanced. When only about 28% by mass of elastomer is used as in example 1, T of PP can be obtained bd Reduced to-40 ℃ and a notched impact strength of about 50kJ/m at-30 DEG C 2 . As the elastomer usage amount is reduced, and simultaneously, the ethylene-propylene ternary rubber is vulcanized and reinforced, and the room-temperature tensile strength of the final material can reach 30MPa.
Detailed Description
The technical scheme of the invention is further described in detail below by combining examples. The scope of the invention is not limited in this respect.
In the embodiment of the invention, the polypropylene used is isotactic polypropylene. However, the kind of polypropylene is not limited to the present invention, and various kinds of polypropylene are suitable for the present invention.
The octyl phenol-formaldehyde vulcanized resin used in the examples is HY-2045 produced by Shanxi chemical institute, and has a hydroxymethyl content of 10-14%. Other commercially available octyl phenol novolac vulcanizates are also suitable for use in the present invention.
Example 1
80 parts by weight of polypropylene, 20 parts by weight of ethylene propylene diene monomer rubber, 10 parts by weight of SEP and 0.25 part by weight of antioxidant 1010 are fed into a main feeding port of a double-screw extruder according to the metering; 0.25 weight part of stearic acid, 0.5 weight part of zinc oxide and 0.08 weight part of stannous chloride are fed from a secondary feeding port of the double-screw extruder according to the metering, the secondary feeding port and the main feeding port are separated by 3 sections of cylinders, and the secondary feeding port is positioned in a melting section. 0.8 part by weight of octyl phenol-formaldehyde vulcanized resin was fed in a metered amount from a third feeding port subsequent to the secondary feeding port, and the feeding port was located in the melting section at a 3-section barrel spacing from the secondary feeding port. The polypropylene alloy with low temperature resistance and high impact resistance is obtained through one-time extrusion. The extrusion condition is that the temperature of the main feeding port is 90 ℃, the temperature of a cylinder body between the main feeding port and the secondary feeding port is 180 ℃, the temperature of the cylinder body between the secondary feeding port and the third feeding port is 200 ℃, the temperature of the cylinder body after the third feeding port is 200 ℃, the temperature of the die is 200 ℃, and the rotating speed of a screw is 80rpm.
Example 2:
80 parts by weight of polypropylene, 20 parts by weight of ethylene propylene diene monomer rubber, 10 parts by weight of SEP and 0.25 part by weight of antioxidant 1010 are fed into a main feeding port of a double-screw extruder according to the metering; 0.25 part by weight of stearic acid, 0.5 part by weight of zinc oxide, 0.16 part by weight of stannous chloride are metered in from a secondary feeding port of the twin-screw extruder, and the secondary feeding port is separated from the main feeding port by 3 barrels. 1.6 parts by weight of octyl phenol-formaldehyde sulphide resin are metered in from a third feeding port following the secondary feeding port, and this feeding port is separated from the secondary feeding port by 3 barrels. The polypropylene alloy with low temperature resistance and high impact resistance is obtained through one-time extrusion. The extrusion condition is that the temperature of the main feeding port is 90 ℃, the temperature of a cylinder body between the main feeding port and the secondary feeding port is 180 ℃, the temperature of the cylinder body between the secondary feeding port and the third feeding port is 200 ℃, the temperature of the cylinder body after the third feeding port is 200 ℃, the temperature of the die is 200 ℃, and the rotating speed of a screw is 80rpm.
Example 3:
75 parts by weight of polypropylene, 25 parts by weight of ethylene propylene diene monomer rubber, 8 parts by weight of SEP and 0.25 part by weight of antioxidant 1010 are fed into a main feeding port of a double-screw extruder according to the metering; 0.3125 parts by weight of stearic acid, 0.625 parts by weight of zinc oxide, 0.15 parts by weight of stannous chloride are metered in from a secondary feed port of the twin-screw extruder, which secondary feed port is spaced from the primary feed port by 3 barrels. 1.5 parts by weight of octyl phenol-formaldehyde sulphide resin are metered in from a third feeding port following the secondary feeding port, and this feeding port is separated from the secondary feeding port by 3 barrels. The polypropylene alloy with low temperature resistance and high impact resistance is obtained through one-time extrusion. The extrusion condition is that the temperature of the main feeding port is 90 ℃, the temperature of a cylinder body between the main feeding port and the secondary feeding port is 180 ℃, the temperature of the cylinder body between the secondary feeding port and the third feeding port is 200 ℃, the temperature of the cylinder body after the third feeding port is 200 ℃, the temperature of the die is 200 ℃, and the rotating speed of a screw is 80rpm.
Example 4:
85 parts by weight of polypropylene, 15 parts by weight of ethylene propylene diene monomer rubber, 15 parts by weight of SEP and 0.25 part by weight of antioxidant 1010 are fed into a main feeding port of a double-screw extruder according to the measurement; 0.1875 parts by weight of stearic acid, 0.375 parts by weight of zinc oxide, 0.15 parts by weight of stannous chloride were metered in from the secondary feed port of the twin screw extruder, and the secondary feed port was spaced 3 barrels from the primary feed port. 1.5 parts by weight of octyl phenol-formaldehyde sulphide resin are metered in from a third feeding port following the secondary feeding port, and this feeding port is separated from the secondary feeding port by 3 barrels. The polypropylene alloy with low temperature resistance and high impact resistance is obtained through one-time extrusion. The extrusion condition is that the temperature of the main feeding port is 90 ℃, the temperature of a cylinder body between the main feeding port and the secondary feeding port is 180 ℃, the temperature of the cylinder body between the secondary feeding port and the third feeding port is 200 ℃, the temperature of the cylinder body after the third feeding port is 200 ℃, the temperature of the die is 200 ℃, and the rotating speed of a screw is 80rpm.
Example 5:
80 parts by weight of polypropylene, 20 parts by weight of ethylene propylene diene monomer rubber, 10 parts by weight of SEPS and 0.25 part by weight of antioxidant 1010 are fed into a main feeding port of a double-screw extruder according to the measurement; 0.25 weight part of stearic acid, 0.5 weight part of zinc oxide and 0.12 weight part of stannous chloride are fed from a secondary feeding port of the double-screw extruder according to the metering, the secondary feeding port and the main feeding port are separated by 3 sections of cylinders, and the secondary feeding port is positioned in a melting section. 1.2 parts by weight of octyl phenol-formaldehyde sulphide resin are metered in from a third feeding port following the secondary feeding port, and the feeding port is located in the melting section, spaced from the secondary feeding port by 3 barrels. The polypropylene alloy with low temperature resistance and high impact resistance is obtained through one-time extrusion. The extrusion condition is that the temperature of the main feeding port is 90 ℃, the temperature of a cylinder body between the main feeding port and the secondary feeding port is 180 ℃, the temperature of the cylinder body between the secondary feeding port and the third feeding port is 200 ℃, the temperature of the cylinder body after the third feeding port is 200 ℃, the temperature of the die is 200 ℃, and the rotating speed of a screw is 80rpm.
The properties of the materials obtained in examples 1 to 5 are shown in Table 1 below:
table 1:
from the melt index of each example in Table 1, the low temperature and high impact resistant polypropylene alloy prepared by the invention has better processability. The melt fingers of the examples meet the requirements of a typical extrusion process for polymer melt fingers.
Further compared with the patent CN 113912948A, the material prepared by the technical scheme of the invention has obviously higher tensile strength than the patent CN 113912948A (about 24 MPa), and does not need to use fumed silica with higher price, thereby greatly reducing the material cost. Meanwhile, the material prepared by adopting the technical scheme of the invention has excellent low-temperature toughness, and the strength and toughness of the material are well balanced. In addition, the phenolic resin is adopted as a vulcanization system, so that the high-temperature degradation of the matrix PP can be avoided, and the material has better secondary processing performance. The material prepared by the invention has better tensile property and impact property than those prepared in the comparative patent.
Compared with the method for jointly toughening the PP by adopting the ethylene-propylene-diene rubber and the SEP disclosed by Polymer 112 (2017) 318-324, the method provided by the invention has the advantages that the unsaturated ethylene-propylene-diene rubber is used for replacing the saturated ethylene-propylene-diene rubber, so that a vulcanization system can be introduced to dynamically vulcanize the ethylene-propylene-diene rubber, and as a result, the elastomer consumption can be greatly reduced when better low-temperature impact performance is realized, and the tensile strength of the material is obviously increased. Polymer 112 (2017) 318-324 requires up to 44% elastomer by mass to convert PP to brittle-to-ductile transition temperature (T bd ) Reduced to-30 ℃ and has a notched impact strength of about 20kJ/m at-30 DEG C 2 The tensile strength at room temperature was about 9MPa. In the invention, ethylene-propylene ternary rubber is used for replacing ethylene-propylene binary rubber, and phenolic resin is used for vulcanizing the ethylene-propylene ternary rubber, and in the embodiment 1, when only about 28 mass percent of elastomer is used, the T of PP can be obtained bd Reduced to-40 ℃ and a notched impact strength of about 50kJ/m at-30 DEG C 2 . As the elastomer usage amount is reduced, and simultaneously, the ethylene-propylene ternary rubber is vulcanized and reinforced, the room-temperature tensile strength of the final material can reach 30MPa, and the toughness and the strength of the material are well balanced.
Claims (10)
1. The dynamic vulcanized low-temperature-resistant high-impact-resistant polypropylene alloy is characterized by comprising the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion;
the thermoplastic elastomer is one or two of a styrene-hydrogenated isoprene copolymer or a styrene-hydrogenated isoprene-styrene copolymer.
2. The dynamically vulcanized low-temperature-resistant high-impact-resistant polypropylene alloy according to claim 1, wherein the mass content of hydroxymethyl active groups in the octyl phenol-formaldehyde vulcanized resin is 5-20%.
3. The dynamically vulcanized low temperature and high impact resistant polypropylene alloy according to claim 1, wherein the low temperature and high impact resistant polypropylene alloy further comprises an antioxidant, and the dynamically vulcanized low temperature and high impact resistant polypropylene alloy comprises the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion
An antioxidant: 0.01 to 5 parts by weight.
4. A dynamically vulcanized high impact and low temperature resistant polypropylene alloy according to claim 3, wherein said high impact and low temperature resistant polypropylene alloy comprises the following components in parts by weight:
polypropylene: 70 to 90 parts by weight
Ethylene-propylene ternary rubber: 5 to 25 parts by weight
Thermoplastic elastomer: 5 to 15 parts by weight
Octyl phenol-formaldehyde cured resin: 0.1 to 3 parts by weight
Stannous chloride: 0.008-0.36 weight portion
Zinc oxide: 0.1 to 0.75 part by weight
Stearic acid: 0.05 to 0.375 weight portion
An antioxidant: 0.01 to 5 parts by weight.
5. A dynamically vulcanized high impact and low temperature resistant polypropylene alloy according to claim 3, wherein said high impact and low temperature resistant polypropylene alloy comprises the following components in parts by weight:
polypropylene: 75-85 parts by weight
Ethylene-propylene ternary rubber: 15 to 25 parts by weight
Thermoplastic elastomer: 8 to 15 weight portions
Octyl phenol-formaldehyde cured resin: 0.5 to 2 weight portions
Stannous chloride: 0.05 to 0.2 part by weight
Zinc oxide: 0.3 to 0.7 part by weight
Stearic acid: 0.15 to 0.35 part by weight
An antioxidant: 0.05 to 2 parts by weight.
6. The dynamically vulcanized low-temperature-resistant high-impact-resistant polypropylene alloy according to one of claims 1 to 5, wherein the amount of the octyl phenol-formaldehyde vulcanized resin is 2 to 12 percent of the mass of the ethylene-propylene ternary rubber;
the dosage of stannous chloride is 8-12% of the mass of the octyl phenolic resin;
the zinc oxide is 2-3% of the mass of the ethylene-propylene ternary rubber;
the dosage of the stearic acid is 1 to 1.5 percent of the mass of the ethylene-propylene ternary rubber.
7. The method for preparing the dynamically vulcanized high impact and low temperature resistant polypropylene alloy according to any one of claims 1 to 5, wherein the method is a fractional step method comprising the following steps:
(1) According to the raw material proportion, polypropylene, ethylene-propylene ternary rubber and a thermoplastic elastomer are fed, and part of stearic acid, part of zinc oxide, part of stannous chloride and part of antioxidant are fed, and are melt-blended by an internal mixer or melt-extruded and granulated by a double screw extruder, so that an intermediate material is obtained;
(2) And (3) melting, extruding and granulating the intermediate material, the rest of stearic acid, the rest of zinc oxide, the rest of stannous chloride and the rest of antioxidant by using a double-screw extruder, putting octyl phenol-formaldehyde vulcanized resin into a melting section of the double-screw extruder for dynamic vulcanization, and extruding and granulating to obtain the low-temperature-resistant high-impact-resistant polypropylene alloy.
8. The method according to claim 7, wherein in the step (1), the added part of stearic acid, part of zinc oxide, part of stannous chloride and part of antioxidant are respectively 50-100% of the total stearic acid, total zinc oxide, total stannous chloride and total antioxidant, and the rest of stearic acid, the rest of zinc oxide, the rest of stannous chloride and the rest of antioxidant are added in the step (2);
the temperature of the internal mixer melt blending in the step (1) is 140-230 ℃, and the temperature of the twin-screw extruder melt extrusion granulation is 140-230 ℃.
9. The method for preparing a dynamically vulcanized high impact and low temperature resistant polypropylene alloy according to any one of claims 1 to 5, wherein said method is a single step method:
for a twin screw extruder equipped with a single metering feed system and capable of achieving segmented feeding, the single step process employed is as follows:
the polypropylene, the ethylene-propylene ternary rubber and the thermoplastic elastomer are fed into a main feeding port of a double-screw extruder according to the measurement; metering stearic acid, zinc oxide and stannous chloride from a main feeding port of a double-screw extruder or from a secondary feeding port of a barrel which is spaced from the main feeding port by at least 1 section; stearic acid, zinc oxide and stannous chloride can be fed from the same secondary feeding port or respectively fed from 2-3 secondary feeding ports, and at least 1 section of cylinder is arranged between every two adjacent secondary feeding ports; feeding octyl phenol-formaldehyde vulcanized resin from a third feeding port arranged in the melting section or the homogenizing section according to the measurement; the third feeding port and the last secondary feeding port are separated by at least 2 sections of cylinders; when the antioxidant is used, the antioxidant can be fed from any feeding port; finally, the low-temperature-resistant high-impact-resistant polypropylene alloy is obtained through one-time extrusion.
10. Use of a dynamically vulcanized low temperature and high impact resistant polypropylene alloy according to any one of claims 1 to 5 for the preparation of automotive bumpers, washing machine liners, refrigerator liners.
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